www.mejournal.

orgJournalofMetallurgicalEngineering(ME)Volume3Issue3,July2014
doi:10.14355/me.2014.0303.05

TheEffectofMolybdenumonthe
TribologicalBehaviorofNfgrey(8)CastIron
AgunsoyeJ.O.1,BelloS.A.1,TalabiS.I.2,HassanS.B.1,MoumohK.I.1
DepartmentofMetallurgicalandMaterialsEngineering,FacultyofEngineering,UniversityofLagos,Akoka,
Lagos,Nigeria
1

DepartmentofMaterialsandMetallurgicalEngineering,FacultyofEngineering,UniversityofIlorin,Ilorin
Nigeria
2

jagunsoye@unilag.edu.ng;1adekunle_b@yahoo.com;2isaacton@yahoo.com,1profsbolajihassan@gmail.com,
olumuyiwawe@yahoo.com,1ebumysunshine4nice@yahoo.com.

*1
3

Received6December,2013;Revised16January,2014;Accepted9February,2014;Published9June,2014
2014ScienceandEngineeringPublishingCompany

Abstract
The effect of molybdenum on the morphological and wear
behaviourofNigeriaFoundriesgreycastiron(8)[NFgrey(8)]
has been studied. The microstructural and mechanical
properties of the cast samples for the control and the
NFGrey(8)/Molybdenum alloy were characterised using
SEM, XRD, Brinell Hardness and impact energy testing
Machine respectively. MATLAB linear curve fitting
technique was used to obtain the approximate linear
equation via first differential approach. The results show
that molybdenum addition improved significantly the wear
resistance of the NFGrey(8) cast iron. However, the
toughness of the alloy was sacrificed. The strong and hard
intermetallic compounds within the matrix are attributable
towearresistanceoftheNFGrey(8)/Moalloy.
Keywords
Tribolology; Wear Coefficient; Impact Energy; Surface Abrasion
andHardness

Introduction
Theexcellentwearresistanceofgreycastironduring
dry sliding at low loading conditions is attributed to
the feeding of the contact surface by graphite flakes
andformationofagraphitefilmonthecontactsurface
(Takeuchi, 1968; Montgomery, 1969; Sugishita, 1981).
Itisgenerallyacceptedthatapearliticstructureofthe
matrix and an ASTM type A graphite flake provides
the best wear resistance for grey cast iron in engine
cylinder bore applications (White, 1992 and Leech,
1983).Generally,wearresistancehasbeenfoundtobe
dependent on matrix microstructure, carbide types
and characteristics (size, morphology, distribution,

126

orientation (Dogan, 1995) and the volume fraction,

fracture toughness and hardness of the alloys (Zum,
1998;Berns,2003;Cetinkaya,2006).Italsodependson
loading conditions, the features of the tribological
environments, the relative movement of the contact
surface and the type and size of the abrasive bodies
(Agunsoyeetal.2013).
Ingreycastironalloy,thegraphitemorphologycanbe
divided into three types: flakelike, vermicularlike
and sphericallike. The alloying elements can modify
the matrix microstructure, graphite morphology and
mechanical properties of grey cast iron alloy. The
siliconandsomerareearthelementscantransformthe
graphite morphology from flakelike to vermicular
like or sphericallike. Different functional alloy cast
irons, such as gray cast iron, spheroidal cast iron,
vermicularcastiron,ductilecastiron,canbeobtained
by adding different alloying elements (Vadiraj et al.,
2010; Abedi, 2010; Xu, 2005 and Matsuo, 2005). The
wear behaviour of grey cast iron containing
manganese has beenstudied and thepresence of the
intermetallic(FeMn)3Cinthegreycastironmatrixhas
improved on the wear property of the grey cast iron
(Agunsoyeetal.2012).
Molybdenumisastrongcarbideformer.About86%of
molybdenum produced is used in metallurgical
applications such as alloys, with the rest of
molybdenum used as compounds in chemical
applications.Theabilityofmolybdenumtowithstand
extremetemperatureswithoutsignificantlyexpanding
or softening makes it useful in applications that

JournalofMetallurgicalEngineering(ME)Volume3Issue3,July2014www.mejournal.org

involve intense heat, including the manufacture of

armor, aircraft parts, electrical contacts, industrial
motors and filaments. It has observed from the
literature that little or no work has been done on the
incorporation of molybdenum in the cast iron.
However, this paper is centered on studying the
effects of the molybedum additions on the the
tribological behaviour and mechanical properties of
theNigerianFoundriesgrey(8)(NFGrey[8])castiron
alloyedwithmolybdenum.

and boiled starch were used to prepare a green sand

mould with a cope and drag moulding boxes in
accordance with BS 14 standard. The mould were
labelledCc,C1,C2C3andC4respectively.Themeltwas
poured(Figure 3) at 1270 70C into the improvised
mouldcavity(seeFigure2).
The first batch of melting that corresponds to control
sample without addition of any solute matter was
pouredintothemouldlabelledC0.

Experimental Methods
A known composition of NFGrey(8)cast iron sourced
fromNigerianFoundries,IlupejuLagosstateNigeria
used to make a melt of grey cast iron without any
addition of ferro molybdenum. The soloidified
productofthismeltservesasthecontrolbatchforthe
study. Subsequent melts of the grey cast iron were
made with incremental addition of molybdenum as
alloying element. The compositional analysis for the
controlsamplerevealedthatitcontains3.32%C,1.89%
Si, 0.33% Mn, 0.12%P, 0.11%S and the remaining
94.24%beingtheiron(Fe).Thesampleswerecastina
localfoundryatNewGarage,Lagos,Nigeriaina60Kg
capacitycruciblefurnace.
Fivecopeanddragsandmouldswereproducedusing
two wooden patterns each of dimensions
12x12x205mmaspresentedinFigure1.

FIG.3:POURINGINTOMOULD

Then, a known quantity of molybdenum granule

corresponding to 2kg was added to the molten grey
cast iron in the crucible and thoroughly stirred with
dry hard wooden stick after which it was poured at
13000C into the mould labelled C1. This process was
repeated for additional three times with increasing
weight(4,6and8kg)ofmolybdenumgranules.After
pouringthemelt,itwasallowedtosolidifyandcoolto
theroomtemperaturewhileinthemouldafterwhich
themouldswerecarefullyknockedout(seeFigure4).

FIG.1:THECOPEANDDRAGMOULD
FIG.4:THEASCASTALLOY

FIG.2:60KGCRUCIBLEFURNACE

A mixture of dried fresh silica sand, bentonite, water

FIGURE5:THEFETTLEDSAMPLE

The cast ingot was wire brushed to remove the sand

grain and gating system was cut off with angle

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www.mejournal.orgJournalofMetallurgicalEngineering(ME)Volume3Issue3,July2014

correspondingvolumelosswascalculatedineachcase.
Theprocesseswererepeatedonthesampleunderthe
sameappliedloadsbuthigherspeed(4.72ms1)ofdisc
rotation. All the process were rerun on the respective
sample sample for each sample of the developed cast
iron. The sliding distance and sliding moments were
calculatedusingequations3and4respectively

grinder. The castings were labelled immediately after

it was fettled, for proper identification. The fettled
greycast/MoalloysamplesispresentedinFigure5.
Representative sample from each cast ingot was
machinedtostandardsamplesforSEM/XRDanalysis,
mechanical properties (impact, hardness) and wear
tests.

iding distance
speed of

The composition of the phase present in the NFGrey

(8)/Mo alloy matrix were analysed with the aid of x
ray diffractometer. The prepared sample was subject
to microstructural analysis to investigate the
morphologyanddistributionofthephasesintheiron
matrix.ScanningElectronMicroscopemodelEVOMA
10LaB6AnalyticalVPSEMat20KVwasused.

The 60 x 10 x 10mm sample of each sample of

developed cast irons was subjected to impact energy
testwiththeaidofAveryDenisonUniversalImpact
Testing Machine to measure its ability to absorb
energyimpactinaccordancewithprovisioninASTM
D25693.
The spectrometric analysis was carried out on the
sample of each sample of the developed cast irons
withtheaidsofHilgerAnalyticalDirectOpticallight
EmissionPolyvacSpectrometerE980C.
Results and Discussion
CompositionalAnalysis

TheslidingwearresistanceoftheproducedNFGrey(8)
cast iron/Mo alloy was investigated with the aid of
pin on discmachine. The initial weight of the sample
before the test and final weight after each test were
measured with the aid of a digital electronic
measuringscalewith0.001accuracy.Aftereachtest,
the wear particles deposited on the emery paper was
blownoffwiththeaidsofairblower.Beforethefinal
weight is taken, the surface of the sample under test
was cleaned with the white cotton wool soaked in
acetone.Thesurfaceofthesamplewasplacedagainst
a 200mm diameter surface with 120m mesh emery
papermountedonthepinondisc,rotatingataspeed
of2.36ms1underanappliedloadof10Nfor60s.The
sameprocedurewasrepeatedonthesamesamplefor
four times keeping the parameters constant and
volume loss was calculated in each case using
equation1.

Figure6showsthedistributionofthephasespresents
in the matrix of the control grey cast iron sample as
obtained from xray diffractometer. The figure
revealed the presence of the following compounds in
the iron matrix: cementite having the highest count
score, followed by carbon iron silicide and other
compounds in that order. (See Table 1). The
compounds formed by the chemical reaction of
metallic components with carbon is as a result of
gradual cooling of the melt from the pouring
temperaturetotheambienttemperature.
Figure7and8representstheXRDphasedistribution
for the NFGrey (8) cast iron with 2kg and 8kg ferro
molybdenum additions respectively. The count score
andchemicalformulaoftheintermetalliccompounds
presentinthematrixispresentedinTable2and3.The
newcompoundsformedsuchasmolybdenumsilicide
(MoSi0.65 and MoSi2) may be attributable to the
presence ofmolybdenum granule in the molten bath
of NFGrey(8) cast iron under gradual cooling of the
melt,themolybdenumatomsreactswithsiliconatoms
tonucleateatomsofthementionedcompounds.Table
4 shows the elemental composition analysis of the
control cast iron and the developed cast irons as
obtainedfromthespectrometer.

Volumeloss=initialweightfinalweight(1)
The average volume loss was calculated using
equation2
1

4 V

The process was repeated on the same sample under

increasingappliedloads(6N,10N,12N,14N,16N)and

128

3
4

Eachsamplepreparedforhardnesstestofeachsample
of NFGrey (8)/Mo alloy cast iron was loaded in
accordancewiththeAmericanSocietyforTestingand
Materials (ASTM E10) to measure resistance of the
materialstosurfaceindentation.TheBrinellHardness
Tester (Dynamic Hardness Tester by Fasne Test
Equipment), Model: DHT6 was used. The test was
carriedoutatfivedifferentpointsonthesurfaceofthe
sampleandtheaverageBrinellhardnessnumberwas
obtainedforeachsample.

Average volume loss

of the disc x time

10

20

5000

30

40

50

60

Fe3 C; Cu0.83 Si0.17; Mo Si2

70

Position[?Theta]
70

Fe3 C; Mo Si2

Fe; Fe3 C

60

Fe3 C
Fe3 C; Mo Si2

d2_13_1274-ver2.raw

Fe3 C

50

Fe3 C; Mo Si0.65
Fe3 C; Si

40

Fe3 C

15000
Fe; Fe3 C

Fe3 C

Fe3 C
Fe3 C
Fe3 C; C0.12 Fe0.79 Si0.09

Fe3 C

Fe3 C; C0.12 Fe0.79 Si0.09; C

Fe3 C; C; Fe

Fe3 C

Fe3 C; Fe

Fe3 C; C0.12 Fe0.79 Si0.09; Mo Si2; C

Fe3 C; C0.12 Fe0.79 Si0.09; C; Fe

Fe3 C; C

Fe3 C; C0.12 Fe0.79 Si0.09

Fe3 C

Fe3 C; C0.12 Fe0.79 Si0.09

Fe3 C; C

10000

Fe3 C; Mo Si0.65

Fe3 C; Mo Si0.65; Cu0.83 Si0.17

Fe3 C

30

Fe3 C; Mo Si0.65

20

Fe3 C; Mo Si0.65

10

Fe3 C; Mo Si2

Mo Si2

Fe3 C; Mo Si2; Fe

JournalofMetallurgicalEngineering(ME)Volume3Issue3,July2014www.mejournal.org

20000
d2_13_1276-ver2.raw

Position[? Theta]
80

80

90

FIGURE6:XRDOFTHECONTROLSAMPLE(NFGREY(8)C0)

10000

90

FIGURE7:XRDOFTHENFGREY(8)C1ALLOYSAMPLE

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www.mejournal.orgJournalofMetallurgicalEngineering(ME)Volume3Issue3,July2014

TABLE1:THECOUNTSCORE,NAMEANDCHEMICALFORMULAOFIDENTIFIEDCOMPOUNDSINTHEMATRIXOFTHECONTROLSAMPLE(NFGREY(8)C0

Score
57
36
44
27

CompoundName
Cementite
CarbonIronSilicon
Graphite
Iron

ChemicalFormula
Fe3C
C0.12Fe0.79Si0.09
C
Fe

TABLE2:THECOUNTSCORE,NAMEANDCHEMICALFORMULAOFIDENTIFIEDCOMPOUNDSINTHEMATRIXOFTHENFGREY(8)C1ALLOYSAMPLE

CompoundName
Iron
Cementite
Silicon
MolybdenumSilicon
CopperSilicon
MolybdenumSilicon

ChemicalFormula
Fe
Fe3C
Si
MoSi0.65
Cu0.83Si0.17
MoSi2

Fe; Fe3 C; Fe3 C

Score
53
46
13
16
16
7

d2_13_1275-ver2.raw

20000

Fe3 C; Fe3 C

Fe

Fe3 C; Cu3 Mo; Fe3 C

Fe3 C
Fe3 C; Fe3 C

Fe3 C; Fe3 C
Cu3 Mo

Fe3 C; Fe3 C
Fe3 C; Fe3 C

Fe3 C; Fe3 C

Fe3 C

Fe3 C; Fe3 C

10000

0
10

20

30

40

50

60

70

80

90

Position[? Theta]

FIGURE8:XRDOFTHENFGREY(8)C4ALLOYSAMPLE
TABLE3:THECOUNTSCORE,NAMEANDCHEMICALFORMULAOFIDENTIFIEDCOMPOUNDSINTHEMATRIXOFTHENFGREY(8)C4ALLOYSAMPLE

Score
46
35
15
24

CompoundName
Iron
CopperMolybdenum
Gupeiite
Cementite

ChemicalFormula
Fe
Cu3Mo
Fe3Si
Fe3C

TABLE4:ELEMENTALCOMPOSITIONALANALYSISOFTHECONTROLANDTHEDEVELOPEDNFGREYIRON(8)/MOLYBDENUMALLOY

130

Samples

Si

Mn

Mo

Cu

Fe

NFGREY(8)Co

3.31

1.88

0.33

0.00

0.12

0.12

0.11

94.13

NFGREY(8)C1

3.30

1.24

0.32

0.02

0.11

0.12

0.13

94.76

NFGREY(8)C2
NFGREY(8)C3
NFGREY(8)C4

3.29
3.32
3.23

1.26
1.27
1.33

0.31
0.29
0.41

0.03
0.04
0.09

0.09
0.13
0.12

0.13
0.11
0.12

0.10
0.12
0.11

94.79
94.82
93.49

JournalofMetallurgicalEngineering(ME)Volume3Issue3,July2014www.mejournal.org

MicrostructuralAnalysis/EDS
Figure 9 shows the SEM micrograph of the control
iron sample and the corresponding EDS in Figure 10.
The dark flakes as indicated in Figure 9 represented
the uniform distribution of graphite in the cast iron
NFGrey(8) for the control sample. The high
concentration of the graphite flakes is attributable to
the low hardness recorded and low wear resistance.
Figure 11 shows the SEM micrograph of the
NFGrey(8)C3 alloy and its corresponding EDS in
Figure12.Thepresenceofmolybdenumisresponsible
fortheincreasepercentageofintermetalliccompounds
such as Cu3Mo, MoSi0.65 and MoSi2 within the
ledeburite matrix as shown in Figure 9. This agrees
with Table 3. The compounds are known to be very
hard phases and their presence within the ledeburite
matrix of the NFGrey(8)/Mo alloy is responsible for
highhardnessandwearresistance.Thisargumentis
collaboratedwith thelower toughnessvalues (impact
energy)asobservedinFigure18.

FIGURE11:SEMMICROGRAPHOFTHE
NFGREY(8)/3%MOLYBDENUMSAMPLE(X200)

FIGURE9:SEMMICROGRAPHOFTHEGREYCASTIRONWITH
NOMOADDITION(X200)

BrinellHardnessNumber

FIGURE12:EDSOFTHENFGREY(8)C3ALLOYSAMPLE

500
450
400
350
300
250
200
150
100
50
0

SAMPLES

FIG.13:HARDNESSVALUESOFTHECONTROLAND
DEVELOPEDNFGREY(8)/MOALLOY

HardnessValues

FIGURE10:EDSOFTHEGREYCASTIRONWITHNO
MOLYBDENUMADDITION

Figure13showstherelationshipbetweentheaverage
brinell hardness number of NFGrey(8)/Mo alloy
with %wt of molybdenum additions. It was
discovered that the hardness values of the developed

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NFGrey(8)/Mo alloy increased as the %wt of

molybdenumincreased.Thismaybeattributedtothe
greaterdegreeofdislocationimpingementbythehard
molybdenum compounds in the iron matrix (see
Tables23).

The MATLAB linear curve fitting was used to obtain

theapproximatelinearequation(seeequations514)of
eachcurveinFigures14and15.
LowSpeedWearCurveEquations
ForNFGrey(8)C4y=2.4X109x+4.1X107(5)

WearAnalysis

ForNFGrey(8)C3y=4.2X109x+1.6X106(6)

Figures 14 and 15 represent the relationship between

volume loss and sliding moment of the developed
Mo/NFG(8) cast iron. Generally, it was observed that
the volume loss increased as the sliding moment
increased. Furthermore, the volume loss decreased as
the percentage molybdenum granules in the cast iron
increased. This may be attributable to increased
hardness of the grey cast iron as the %wt of the
molybdenum granules addition increased and high
wear resistance of the molybdenum carbides.
However, incorporation of molybdenum in the
NFGREY(8)castironimprovedthewearresistanceof
thegreycastiron(NFGrey[8]).Howevertheproduced
NFGrey(8)/Moalloyisanexcellentmaterialforwear
resistance application especially in quarry where
impactisconsideredminimumi.ebottomorsideplate
andoccasionallyasmachinebedframe.

ForNFGrey(8)C2y=4.7X109x+1.7X106(7)
ForNFGrey(8)C1y=5.0X109x+2X106(8)
ForNFGrey(8)C0y=6.7X109x+1.1X106(9)
HighSpeedWearCurveEquations
ForNFGrey(8)C4y=1.8X109x+3.8X107(10)
ForNFGrey(8)C3y=2X109x+1.1X106(11)
ForNFGrey(8)C2y=1.9X109x+2.7X106(12)
ForNFGrey(8)C1y=2.4X109x+2.8X105(13)
ForNFGrey(8)C0y=2.9X109x+2.7X106(14)
-9

Wear Coefficient (Cm3/N.m)

-6

x 10

Fe/4Mo
Fe/3Mo
Fe/2Mo
Fe/1Mo
Fe

V olum e Los s (cm 3)

7
6

x 10

Fe/4Mo
Fe/3mo
Fe/2Mo
Fe/1Mo
Fe

6
5
4
3
2
1

2.5

3.5
4
Speed (ms-1)

4.5

FIG.16:WEARCOEFFICIENTOFTHEDEVELOPEDNFGREY
(8)/MOLYBDENUMALLOYWITHSPEED

4
3

2
1
400

500

600

700
800
900
Sliding Moment (N.m)

1000

1100

Wear resistance (N.m/cm3)

6
1200

FIG14:WEARLOSS(CM3)WITHSLIDINGMOMENT(N.M)OF
THEDEVELOPEDNFGREY(8)/MOALLOYAT2.36MS1
-5

x 10

Volume Loss (cm3)

0.8

0.6

Fe/4Mo
Fe/3Mo
Fe/2Mo
Fe/1Mo
Fe

1200

1400
1600
1800
Sliding Moment (N.m)

2000

2200

2400

FIG.15:WEARLOSS(CM3)WITHSLIDINGMOMENT(N.M)OF
THEDEVELOPEDNFGREY(8)/MOAT4.72MS1

132

2.36ms-1
4.72ms-1

3
2
1
0

0.5

1.5

2.5
wt% Mo

3.5

The wear coefficient, a significant parameter in

measuring the wear resistance of the material was
estimatedfromtheequationusingthefirstdifferential
approach. The graph of wear coefficient versus speed
wasplottedtoinvestigatetheeffectofthespeedonthe
wearbehaviourofthedevelopedNFGrey(8)/Moalloy
(see Figure 16). Generally, it was discovered that the
wear coefficients of the developed NFGrey (8)/Mo

0.2

1000

FIGURE17:WEARRESISTANCEOFNFGREY(8)/MOALLOY
WITH%WTOFMOLYBDENUMADDITIONS

0.4

0
800

x 10

JournalofMetallurgicalEngineering(ME)Volume3Issue3,July2014www.mejournal.org

alloydecreasedasthespeedofdiscrotationincreased.
Hence, the NFGrey (8)/Mo alloy materials developed
moreresistancetosurfaceabrasionasthespeedofthe
disc rotation and wt% of molybdenum increased (see
Figure17).Itwasalsoobservedthatthetypeofphases
present and their characteristics influences the wear
behaviour of grey cast iron. This observation agrees
withAgunsoyeetal,2013.
ImpactEnergy

ImpactEnergyValues(J)

Figure 18 shows the relationship between the impact

energies of NFGrey (8)/Mo alloy and %wt of ferro
molybdenum additions. It was observed that the
impact energy decreased as the wt% of molybdenum
increased.Theincorporationofmolybdenumgranules
inNFGrey(8)castirongreatlyembrittlesit.
9
8
7
6
5
4
3
2
1
0

abrasion increased as the speed of disc rotation

increased.
5. Wear resistance of developed cast irons increased
as%wtofmolybdenumadditionincreased.
6. Hence, the NFGrey(8)/Mo alloy can be used in a
wear resistant applications such as in bottom or
sideplateofajawcrusherorbedframeforalathe
machine where impact load is considered
minimum.
ACKNOWLEDGEMENT

The authors wish to acknowledge the valuable

contribution of Raheem I. A of Physics Department,
UniversityofLagos,AkokaLagosforhisassistancein
carryingoutsometests.
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